International Journal of Engineering Science 101 (2016) 110114

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International Journal of Engineering Science

journal homepage: www.elsevier.com/locate/ijengsci

Nonlocal uid mechanics description of solvation forces

Kanzo Okada a,, Masaru Sugiyama b
a
b

Institute of Mathematics for Industry, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 8190395, Japan
Graduate School of Engineering, Nagoya Institute of Technology, Gokiso-cho, Showa-ku, Nagoya 4668555, Japan

a r t i c l e

i n f o

Article history:
Received 18 November 2015
Revised 6 January 2016
Accepted 17 January 2016

a b s t r a c t
In this paper an analytical expression for the solvation force, based on the nonlocal surface
stress due to the nonlocal density variation, is constructed by making a surface functional
approximation to the general stress constitutive equation of nonlocal viscous uids. It is
then applied to derive a well-known semi-empirical expression for solvation forces.
2016 Elsevier Ltd. All rights reserved.

Keywords:
Solvation forces
Nonlocal uid mechanics
Nonlocal density variation
Nonlocal surface stress residual
Radial distribution function

1. Introduction
Solvation forces manifest themselves in thin uid lms of less than several molecular diameters between the molecularly
smooth solid surfaces. They are experimentally known to oscillate with distance with a spatial periodicity roughly equal to
the diameter of a solvent molecule and die out within a range of a few molecular diameters. A solvation force is also known
to arise once there is a variation in the uid density at the surfaces as they approach each other. The uid density at each
surface is observed to vary around its bulk value due to the restructuring of layers of uid molecules near the surfaces as
they close in. For this reason, the solvation force is also called the oscillatory structural surface force. For the details, see
Israelachvili (2011) and the literature quoted therein.
The theoretical studies of solvation forces have been carried out using computer simulations (e.g., Snook & van Megan,
1980), the integral equations of statistical mechanics (e.g., Attard & Parker, 1992), and semi-empirical models (Kralchevsky &
Denkov, 1995), stimulating and advancing the experimental measurements, and vice versa. In this paper we propose another
approach based on nonlocal uid mechanics to the theory of solvation forces.
Nonlocal uid mechanics proposed by Eringen (1972) is inherently endowed with the so-called localization residuals that
arise in localizing the global balance laws and can be applied to a wide range of physical phenomena where the external
characteristic length (e.g., lm thickness) and the internal characteristic length (e.g., molecular diameter) are of the same
order (Eringen, 2002). In this paper we focus on the nonlocal surface stress residual associated with the global law of
balance of linear momentum. This localization residual does not produce any resultant when integrated over the surface of
the body, namely it is the stress at a point of the surface caused by the presence of the rest of the surface. This means that
the nonlocal surface stress residual contains none other than spatially uctuating components. It also gives the nonlocal part
of surface traction. Thus, solvation forces may be represented on a continuum basis by the nonlocal surface stress residual.

Corresponding author. Tel.: +81 928024479.

E-mail address: okada@imi.kyushu-u.ac.jp (K. Okada).

http://dx.doi.org/10.1016/j.ijengsci.2016.01.001
0020-7225/ 2016 Elsevier Ltd. All rights reserved.

K. Okada, M. Sugiyama / International Journal of Engineering Science 101 (2016) 110114

111

In Section 2, we construct an analytical expression for the solvation force, based on the nonlocal surface stress due to
the nonlocal density variation, by making a surface functional approximation to the general stress constitutive equation of
nonlocal viscous uids. It is then applied in Section 3 to derive the well-known semi-empirical expression for solvation
forces due to Israelachvili (2011), followed by a concluding remark in Section 4.
2. Nonlocal description of solvation forces
At an isolated solid-uid interface, the geometric constraining effect of the wall on uid molecules causes the latter to
lie in semi-ordered layers at the surface. The formation of these layers has been experimentally observed through density
oscillations propagating at several molecular diameters into the uid (e.g., Israelachvili, 2011). This tendency towards stratication is further augmented at a solid-uid-solid interface by the constraining effect due to the presence of still another
surface. Oscillatory solvation forces arise from a modication in the density of uid molecules at the surfaces induced by the
molecular packing effect associated with a repeated occurrence of the ordering of uid molecules at surfaces followed by the
disruption of this ordering during the approach of a second surface. The solvation force acting on two surfaces separated by
a narrow gap of uid is known to be directly proportional to the increase in the density of uid molecules at each surface
with the proportionality constant being the thermal energy per molecule as they approach each other (e.g., Israelachvili,
2011). This is basically the mechanism to explain the exponentially decaying oscillatory force proles characteristic of solvation forces between two surfaces. It is now well-recognized that this damped oscillating behavior of solvation forces has the
same origin as the radial distribution function and the potentials of mean force which are basic to the statistical mechanical
descriptions of molecular interactions in pure uids and uid mixtures.
On the other hand, solvation interactions that arise in thin uid lms of a few molecular diameters or so between two
surfaces are strongly nonlocal, namely the size of a uid molecule is comparable with the geometric scale of uid lm. In
the eld theories of nonlocal continua, the constitutive theory is formulated in terms of response functionals that describe
the state of a material medium at each point by the knowledge of the independent constitutive variables at all points of
the medium, sometimes known as spatial dispersion. For nonlocal Stokesian uids of Eringen (1972), the dependence of the
free energy on the relative uid density in the vicinity of a point, namely the nonlocal density variation, is included to take
account for such nonlocal surface effects as the surface tension, etc. Rigorous thermodynamics arguments together with the
dependency of the free energy on the nonlocal density variation lead to the stress constitutive equation as a functional of
the nonlocal density variation as one of its arguments. This is consistent with the general view that the oscillatory solvation
forces measured in several uids are attributed to the free energy change associated with the molecular packing effect
(Attard & Parker, 1992).
We write down the law of balance of linear momentum in local form due to Eringen (1972) for the reader to refer to in
the current and succeeding sections since it is the only law of balance relevant to our present study.

tkl,k + ( fl u l ) + fl = 0 in B ,



tkl Fkl + ul (uk k )nk = 0



on

(2.1)

(2.2)

Here, B = material body, =mass density, uk =velocity vector, k =velocity of the discontinuity surface , nk =positive unit
normal to the surface , fl =body force vector, tkl =stress tensor, fl =nonlocal body force residual, the superposed dot denotes material time rate, [[]] = jump of its enclosure at a discontinuity surface , and Fkl =nonlocal surface stress residual.
The nonlocal surface stress residual Fkl is subject to the restriction that it becomes zero upon averaging over the discontinuity surface or the surface B of the material body when the discontinuity surface coincides with it, that is,

Fkl nk dS = 0.

(2.3)

Following the method of Speziale and Eringen (1981) developed for the treatment of wall turbulence, we take a phenomenological approach to model solvation forces by assuming that they are stresses which can determined from the relative mass density in the neighborhood of a point in the material body. In mathematical terms, this means that the solvation
force is a functional of the mass density difference over space, that is,

Fkl (x ) = Fkl [ (x |x ) (x ), x, t]

x, x B.
x

(2.4)

(x |x)

Here, B is the volume occupied by the uid, B is a nonlocal point while x B is a local point of reference, and
is
the mass density at x , given the mass density at x, Hence, the stress at a given point x is determined by the mass density
at all points x of B.
Considering the short-range solvation interaction, within a range of a few molecular diameters, between two surfaces in
a uid and also using the justication given by Speziale and Eringen (1981), we may construct a surface functional theory
to represent the solvation force as the nonlocal surface stress. We thus have

Fkl (x ) = Fkl [ (x |x ) (x ), x x],

x B, x B.

(2.5)

Here, B is the boundary of the body B and x is restricted to within a thin layer at the boundary B. It is to be noted that
invariance under a time shift eliminates the explicit time dependence of Eq. (2.5) on time t.

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K. Okada, M. Sugiyama / International Journal of Engineering Science 101 (2016) 110114

Using the integral representation theorem of Friedman and Katz (1966) for nonlinear functionals, Eq. (2.5) takes the form

Fkl (x ) =


B

klm (r, )dS m ,

(2.6)

where = x x, r (x ) = (x |x ) (x ),and dSm is the m-th component of the area vector dS .
Since r is a scalar quantity and is the relative position vector, they are frame-indifferent. As shown by Speziale and
Eringen (1981), the invariance of Eq. (2.6) under arbitrary time dependent rotations and translations of the spatial frame of
reference and shift in the origin of time requires that klm must be an isotropic tensor function of its arguments.
From the theory of invariance (Spencer, 1971), it can be shown that for the isotropic tensor we have

klm = 0 (r, || )m kl + 1 (r, || )(k lm + l km ) + 2 (r, || )k l m

(2.7)

with the symmetry property

klm = lkm.

(2.8)

Hence, we obtain a nonlinear theory of the form

Fkl (x ) =




0 (r, || )kl dS + 1 (r, || ) k dS l + l dS k + 2 (r, || )k l dS .

(2.9)

When the nonlocal surface stress Fkl given by Eq. (2.9) is integrated with respect to the local point x over the boundary

B, it can be shown that



Fkl (x )dSl = 0,

x B.

(2.10)

Here, we omit the proof of Eq. (2.10) since a similar proof is already given by Speziale (1978) for the case where another
type of surface stress is treated as a functional of a scalar measure dened by taking the inner product of the velocity
difference between two different points and their relative position vector . It is to be pointed out here that in order for
Eq. (2.10) to be satised identically, it is necessary to take

0 (r, || ) = 1 (r, || ),

(2.11)

assuming that 0 and 1 are continuous functions over the domain of denition. Thus we have

Fkl (x ) =





0 (r, || ) kl dS + k dS l + l dS k + 2 (r, || )k l dS ,

(2.12)

where the nonlocal moduli 0 (r, ||) and 2 (r, ||) attenuate sharply to zero with distance ||, subject to the Axiom of
Neighborhood of Eringen (1980). Regarding Eq. (2.10) , it should be stressed that the surface stress Fkl meets the restriction
inherent in the nonlocal surface residuals in general, namely the total resultant stress on the whole surface that arises
because of Fkl (x ) at each point of B must vanish. It is the stress at a point of the surface caused by the presence of the
rest of the surface.
It is reasonable to assume for homogeneous and isotropic uids that the distance of attenuation is the same for the
moduli 0 and 2 . Under this assumption and using the property of nonlocal effects that they die out only short (e.g., a
few atomic or molecular) distances away from a local point x, since with each directional indicator k these moduli are
multiplied by the distance of attenuation , 2 having a factor k l must be negligible as compared to 0 having no such
factor. We thus have

Fkl (x ) =




0 (r, || ) kl dS + k dS l + l dS k .

(2.13)

We go one step further to construct the linear theory from Eq. (2.13) by expressing 0 (r, ||) as a linear function of the
nonlocal density variation r. A simple calculation yields

Fkl (x ) =




0 (|| )r kl dS + k dS l + l dS k .

(2.14)

As the gap between two surfaces becomes zero, so does the uid density at the surfaces. In this limit, according to
Israelachvili (2011), the solvation force approaches to a nite value given by

kT kT/d3 ,

(2.15)

where is the bulk number density of the uid, k is Boltzmann constant, T is the absolute temperature and d is the
molecular diameter. Dimensional considerations together with the limiting condition (2.15) then yield

Fkl (x ) =


B



kT
0 (|x x|/l )N[ (x |x ) (x )] kl dS + k dS l + l dS k ,
l3

(2.16)

where 0 is dimensionless, l should be taken as a length scale, and N denotes the number of molecules per unit mass. Note
that there are N (x) molecules per unit volume at x.

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113

In reference to Eq. (2.16) valid for the structure of uids adjacent to solid surfaces, the product of the number of
molecules per unit mass N at any point x between two surfaces and the uid density difference, (x |x ) (x ), is integrated with respect to x over the surfaces, with a coverage of x being restricted by the nature of the nonlocal modulus
0 , to give the number of molecules at the surfaces found in excess or short of the number of molecules at x. In view of
molecular interactions that actually take place in a uid, N[ (x |x ) (x )] should be represented more accurately and practically by N (x )[g(|x x| ) 1] where g(|x x| ) is the radial distribution function of the uid. By putting it into Eq. (2.16)
, we obtain the nonlocal surface stress at any point x between two surfaces. Thus, Eq. (2.17) gives the nal form of nonlocal
surface stress in the linear theory.

Fkl (x ) =


B

kT
0 (|x x|/l )N (x )[g(|x x|/l ) 1]
l3

kl dS + k dS l + l dS k

(2.17)

When Eq. (2.17) is evaluated at a point x on the surface, it becomes the nonlocal surface stress residual, yielding the
nonlocal surface traction in conformity with the physics of solvation forces as described above.
3. Derivation of a semi-empirical expression for solvation forces
Kralchevsky and Denkov (1995) proposed a semi-empirical expression for the solvation force as the zeroth-order effect,
representing the dependence of the solvation force on both the oscillatory period and the decay length in addition to the
molecular size. In this section, we use the expression given by Israelachvili (2011) where the above three parameters coincide with each other, since we believe it to be sucient to serve the purpose of the paper. It takes the simple form

P (h ) kT cos

h
2 h
exp
,
d
d

(3.1)

where h is the gap width, is the bulk number density of the uid, k is Boltzmann constant, T is the absolute temperature,
and d is the molecular diameter.
We derive from Eq. (2.17) the well-known semi-empirical expression (3.1) for the solvation force in planar geometry.
Once this is done, it can be used to calculate the solvation force between spheres or crossed cylinders immersed in a uid
through the Derjaguin approximation (Derjaguin, 1934), which relates the force between bodies with curved surfaces to the
interaction free energy per unit area between at plane walls in a very simple way.
In order to derive the solvation force between plane walls, we consider a uid bounded by two parallel plates of innite
extent, separated by a small gap h. We are interested in the surface force acting between the plates along the transverse
direction, namely the normal component of the nonlocal surface stress Fkl . When Eq. (2.17) is written in the rectangular
coordinates, it takes the form

Fzz (x ) =

3kT
0 (|x x|/l )N (x )[g(|x x|/l ) 1]
2
B l

z z
dx dy ,
l

(3.2)

where B consists of two at plates dened by z = h/2, x = (x , y , z ), x = (x, y, z ), and |x x| is the distance in the
sense of Euclidean norm.
Making the coordinate variables dimensionless by dividing each by the length scale l, we can write Eq. (3.2) as

Fzz (x ) = 3kT


B



0 (|x x| )N (x )[g(|x x| ) 1] z z dx dy ,

(3.3)

Here, both the primed and unprimed coordinates are now dimensionless.
Since in this particular problem the mass density (x) varies only in the direction normal to the plates, Eq. (3.3) can be
written as

 



Fzz (z ) = 3kTa z z N (z ) g z z 1 z z
where

a z z


B



0 (|x x| )dx dy .

(3.4)

(3.5)

It is to be understood that the quantities enclosed in the brace bracket of Eq. (3.4) are to be evaluated at the plates, i.e.,
z = h/2l.
Nonlocal effects die out sharply with distance. An exponential decaying function is one of the simplest such forms that
can be selected. Hence, we take

a z z =



1
exp z z ,

|z z|

where and are dimensionless constants to be determined.

(3.6)

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K. Okada, M. Sugiyama / International Journal of Engineering Science 101 (2016) 110114

Evaluating the right-hand side of Eq. (3.4) at the upper plate z = h/2l, we obtain

3kT

h/2l z
|h/2l z|

exp(|h/2l z| )N (z )[g(|h/2l z| ) 1].

(3.7)

Similarly, we evaluate it at the lower plate z = h/2l to get

3kT

(h/2l + z )
|h/2l + z|

exp(|h/2l + z| )N (z )[g(|h/2l + z| ) 1].

(3.8)

Subtracting expression (3.8) from expression (3.7), we have

3 kTexp( h/2l )N (z )[exp( z )[g(|h/2l z| ) 1] + exp( z )[g(|h/2l + z| ) 1]].

(3.9)

At this stage, we take the liberty of choosing the length scale l as one-half of the molecular diameter, i.e., l = d/2. Since
at equilibrium the surface force must be uniform throughout the gap, it is independent of z. It then follows that the nonlocal
surface force acting between the plates having a gap width of h/d = O(1 ) can be calculated conveniently at the mid-plane
between the plates, i.e., at z = 0 to get

Fzz (h ) = 6 kTexp( h/d )N (0 )[g(h/d ) 1].

(3.10)

For consistency with the fact that the radial distribution function vanishes in the region near contact and the wellestablished limiting condition (2.15), N (0) in Eq. (3.10) should be taken as the bulk number density of the uid so that

Fzz (h ) = 6 kTexp( h/d )[g(h/d ) 1].

(3.11)

Outside the region near contact, the radial distribution function of a uid of molecules obeying for example a LennardJones 6-12 potential is known from the molecular dynamic calculations of Verlet (1968) to be of the damped oscillating
form

g(h/d ) cos (2 h/d )exp(h/d ) + 1.

(3.12)

Thus, outside the near-contact region where Fzz (h ) assumes the value given by the left-hand side of the limiting condition
(2.15) with an appropriate choice of the parameter , it clearly takes an expression of the same form as the semi-empirical
expression (3.1) for the exponentially decaying oscillatory solvation force, as can be seen by inserting Eq. (3.12) into Eq. (3.11)
with the two tting parameters and .
We plan to solve a specic boundary value problem using the full nonlocal formula (2.17) in a nonplanar geometry in a
sister paper to come.
4. Conclusions
In this paper the theory of solvation forces was examined from a nonlocal continuum point of view to show that a
general expression for the solvation force can be obtained by way of making a surface functional approximation to the
general stress constitutive equation of nonlocal viscous uids. The nonlocal surface stress constructed as a functional of the
nonlocal density variation at the uid boundary was shown to be indeed a nonlocal surface stress residual when evaluated at
a point on the boundary. Since the nonlocal surface stress residual gives the nonlocal part of surface traction, we believe that
the origin of short-range solvation forces is attributable to the nonlocal density variation at a solid-uid interface and that
Eq. (2.17) constructed as such should provide a general analytical expression for the oscillatory solvation force in arbitrary
geometries, with its validity demonstrated in Section 3 through a derivation of the well-known semi-empirical expression
for the solvation force in planar geometry from the linear theory developed.
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